AU2008278272A1 - Biocidal polyacrolein composition - Google Patents
Biocidal polyacrolein composition Download PDFInfo
- Publication number
- AU2008278272A1 AU2008278272A1 AU2008278272A AU2008278272A AU2008278272A1 AU 2008278272 A1 AU2008278272 A1 AU 2008278272A1 AU 2008278272 A AU2008278272 A AU 2008278272A AU 2008278272 A AU2008278272 A AU 2008278272A AU 2008278272 A1 AU2008278272 A1 AU 2008278272A1
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- AU
- Australia
- Prior art keywords
- polyacrolein
- particles
- microns
- size
- particulate
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- Abandoned
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- 239000000203 mixture Substances 0.000 title claims description 57
- 230000003115 biocidal effect Effects 0.000 title claims description 40
- 239000002245 particle Substances 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 14
- 239000003139 biocide Substances 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000003801 milling Methods 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 5
- 238000009472 formulation Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000002195 soluble material Substances 0.000 claims description 4
- 239000010419 fine particle Substances 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 150000005846 sugar alcohols Chemical class 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 239000007900 aqueous suspension Substances 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000002562 thickening agent Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 22
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 description 4
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 4
- 230000000845 anti-microbial effect Effects 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 239000008101 lactose Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000006070 nanosuspension Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- -1 aromatic alcohols Chemical class 0.000 description 2
- 239000000679 carrageenan Substances 0.000 description 2
- 229920001525 carrageenan Polymers 0.000 description 2
- 235000010418 carrageenan Nutrition 0.000 description 2
- 229940113118 carrageenan Drugs 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 208000018522 Gastrointestinal disease Diseases 0.000 description 1
- 206010061217 Infestation Diseases 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004036 acetal group Chemical group 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 208000010643 digestive system disease Diseases 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- 208000018685 gastrointestinal system disease Diseases 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Fodder In General (AREA)
Description
WO 2009/009828 PCT/AU2008/001032 1 BIOCIDAL POLYACROLEIN COMPOSITION This application claims the benefit of priority from US Provisional 60/929961 (19 July 2007) the contents of which are herein incorporated by reference. 5 Field This invention relates to a biocidal polyacrolein composition, to a method of preparing a biocidal polyacrolein composition and to a process for controlling microbial growth using the composition. 10 Background The biocidal properties of polyacrolein are discussed in US Patent 5290894. The poor physical stability of compositions of polyacrolein in water make it difficult to formulate. These problems are reportedly overcome by including 15 hydrophilic comonomers. US Patent 6723336 discloses a water soluble polyacrolein which is useful in treating gastrointestinal disease in animals. Our US Patents 6803356 and 6410040 also disclose methods of improving the solution stability and antimicrobial activity of polyacrolein by modifying the polymer to include acid groups and optionally further reacting the polymer to 20 form acetal groups. Summary We have now found that polyacrolein in the form of finely divided particles of size no more than 30 microns, preferably no more than 5 microns and still 25 more preferably no more than 1 micron form a stable dispersion in water and have a high level of biocidal activity. Accordingly we provide a biocidal composition comprising fine particles comprising polyacrolein wherein at least 90% by weight of particles are of a 30 size no more than 30 microns. Preferably at least 90% by weight of particles are of size no more than 5 microns and still more preferably at least 90% of particles are of size no more than 1 micron.
WO 2009/009828 PCT/AU2008/001032 2 In one embodiment the composition is in the form of an aqueous suspension comprising suspended particles comprising polyacrolein of the above referred particle size. 5 In a further embodiment the invention provides a biocidal composition comprising water dispersible particles comprising a particulate water soluble material and associated there with biocidal particles comprising polyacrolein wherein at least 90% by weight of particles are of a size no more than 30 microns. Preferably at least 90% by weight of particles are of size no more 10 than 5 microns and still more preferably at least 90% by weight of particles are of size no more than 1 micron. The invention further provides a method of preparing a particulate biocide containing polyacrolein in accordance with the above defined composition, the 15 method comprising: (i) forming a solution of polyacrolein in a solvent at least partly soluble in water; and (ii) mixing the solution of polyacrolein with an aqueous composition to provide a fine suspension of polyacrolein particles in the aqueous composition. 20 The invention further provides a method of preparing a particulate polyacrolein biocidal composition comprising milling polyacrolein to reduce the particle size so that at least 90% of particles are of a size no more than 30 microns. Preferably at least 90% of particles are of size no more than 5 microns and still 25 more preferably at least 90% of particles are of size no more than 1 micron. Detailed Description The polyacrolein particles in accordance with the invention comprise at least 90% by weight of particles which are of a size no more than 30 microns. 30 Preferably at least 90% by weight of particles are of size no more than 5 microns and still more preferably at least 90% by weight of particles are of size no more than 1 micron. The polyacrolein particles are typically of size of at least 5 nm more preferably at least 10 nm and most preferably at least 20nm. The optimum particle size depends to a certain extent on the application in WO 2009/009828 PCT/AU2008/001032 3 which the composition is to be used however typically from an activity perspective the more preferred size provides at least 90% by weight of particles of size no more than 200nm and most preferably no more than 150nm. We have found that the activity of particles in the nanoparticle range 5 (up to 1000nm), more preferably no more than 200 nm and particularly up to 150nm is significantly improved. The polyacrolein may be an acrolein homopolymer or copolymer comprising, for example up to 15% and preferably no more than 10% by weight of 10 monomers other than acrolein. Most preferably the polyacrolein is an acrolein homopolymer. The polyacrolein may be formed by radical polymerization, anionic polymerization or based catalysed polymerization. We have found that 15 polyacrolein particles comprising polyacrolein formed by base catalysis exhibit superior activity particularly when compared with polyacrolein prepared by radical polymerization. The polyacrolein particles may be oxidized so as to modify the polymer to 20 include a select proportion of acid groups such as from 0.5 to 5 mole carboxylic acid groups per kilogram of polymer. The incorporation of acid groups by oxidation of a solid in air or other source of oxygen is described, for example in our US Patent 6723336 in Example 1 b. 25 In one aspect the invention provides a method of preparing a particulate polyacrolein biocidal composition in accordance with the above the method comprising (i) forming a solution of polyacrolein in a solvent at least partially soluble in water; and 30 (ii) mixing the solution of polyacrolein with an aqueous composition to provide a fine suspension of polyacrolein particles in the aqueous composition The process provides the particulate polyacrolein in the form of a nano suspension. The nanoparticles may if desired be collected from the nano suspension but generally speaking it is preferred in this embodiment for the WO 2009/009828 PCT/AU2008/001032 4 aqueous nanosuspension to be used in formulation of the biocide optionally with addition of suitable excipients and adjuvants for the desired application. The solvent is preferably at least partly soluble in water. Typically it will have a solubility in water of at least 1% at 20 C. Examples of suitable solvents include 5 aliphatic and aromatic alcohols and ethers and mixtures of two or more thereof where the solvent composition has the required solubility. Specific examples include C1 to C4 alkanols, benzyl alcohol, polyols such as polyethylene glycol and propylene glycol and ethers such as tetrahydrofuran 10 The invention further provides a method of preparing a particulate polyacrolein biocidal composition comprising milling a solid comprising polyacrolein to reduce the particle size so that at least 90% of particles are of a size no more than 30 microns. Preferably at least 90% of particles are of size no more than 5 microns and still more preferably at least 90% of particles are of size no 15 more than 1 micron. The milling may be carried out using various known equipment such as ball mills attrition mill, fluid energy mills and the like. Fluid energy mills are particularly preferred. Milling may be carried out on the solid or a dispersion of 20 the solid in a suitable liquor such as water (in which the solid is insoluble) or a suitable oil. The polyacrolein will typically be milled from a composition having a particle size greater than 5 microns, preferably greater than 50 microns and most 25 preferably greater than 100 microns to provide a particle size wherein at least 90% of particles are of size no more than 5 microns and still more preferably at least 90% of particles are of size no more than 1 micron. In a particularly preferred embodiment of the invention the particulate biocide 30 is formulated as a water dispersible granular or water dispersible powder formulation. Such a formulation may include additives such as dispersants, surfactants, fillers such as clays and metal salts, water soluble materials, thickeners and the like. In one embodiment the particulate polyacrolein is adsorbed onto a carrier which is preferably a water soluble particulate carrier WO 2009/009828 PCT/AU2008/001032 5 such as selected from the group consisting of saccharides, sugar alcohols and water soluble salts such as sodium chloride. Specific examples of sugar and sugar alcohol carriers include lactose, mannose, sucrose, maltose, sorbitol, manitol. Particulate lactose is particularly preferred. Typically the solid 5 particulate carrier for the particulate polyacrolein has a particle size substantially greater than the polyacrolein particles. The water soluble particulate carrier may, for example have a particle size in the range of from 30 to 2000 microns and more preferably from 50 to 500 microns. 10 The polyacrolein will typically comprise at least 10%, preferably at least 25%, still more preferably 50% and most preferably at least 80% by weight of polyacrolein based on the total weight of the particulate biocide composition. The particulate biocide composition may be part of a water dispersible composition in which case it will typically constitute in the range of from 1 to 15 99%by weight and preferably from 1 to 20% by weight of the total water dispersible composition. The compositions of the invention have a number of antimicrobial uses. They are useful in (a) animal feed to treat or reduce the incidence of gastrointestinal 20 disease; (b) in antiseptic and disinfectant preparations; (c) in fungicides in treating or preventing fungal infestation in wood, soil, building materials or plants; (d) as preservatives in cosmetic and pharmaceuticals; and (e) as water treatment preparations for water filters, water cooling towers, water remediation and treatment of domestic or industrial water supplies. 25 The invention will now be described with reference to the following examples. It is to be understood that the examples are provided by way of illustration of the invention and that they are in no way limiting to the scope of the invention. 30 Examples Particle size analysis has been determined using Dynamic Light Scattering with laser diffraction in which method, particle sizes of a dilute suspension of the solid in water are measured between 0.02 and 2000 um.
WO 2009/009828 PCT/AU2008/001032 6 Example 1 Part (a) This Example relates to preparation of a particulate polyacrolein of one aspect 5 in accordance with the invention by a method in accordance with a further aspect of of the invention in which a solution of polyacrolein in a water soluble liquid is added to an aqueous composition. The polyacrolein used in this Example was prepared in accordance with 10 Example 1 b of US Patent 6723336 and was in the form of an oxidized particulate poly(2-propenal, 2-propenoic acid) comprising in the range of from 0.5 to 5 moles of carboxyl groups per kilogram of polyacrolein. The particulate starting material comprised particles of size of about 10 to 15 2000 microns and was insoluble in water. A 20% w/w solution of poly(2-propenal, 2-propenoic acid) in benzyl alcohol was prepared by stirring the mixture at 65 QC and the stirred mixture allowed to cool to room temperature to provided a clear viscous solution. A small volume 20 of ethanol was added and the mixture was added slowly to a vigorously stirred volume of water. The resulting composition was in the form of a nanoparticles of poly(2-propenal, 2-propenoic acid) dispersed in an aqueous mixture and appeared as a transparent mixture of milky appearance. 25 Part (b) This Example examines the biocidal properties of a nanoparticulate dispersion of poly(2-propenal, 2-propenoic acid) The 20% solution of poly(2-propenal, 2-propenoic acid) in benzyl alcohol 30 (97.98 mg) was mixed with absolute ethanol (500 pL) and the mixture added to stirred water (6.9g) in a glass vial. The resulting suspension was backwashed. The final weight was made up with water to 9.979g (ie 2000 ppm active).
WO 2009/009828 PCT/AU2008/001032 7 As a control sample benzyl alcohol (82.4 ml) and ethanol (500 PL) were combined and transferred to water (74g) and made up to 10 g with water. Both active and control samples were subject to antimicrobial testing. Sample MIC (E. coli) Invention 62.5 ppm Control 1000 ppm 5 Example 2 Part (a) A sample poly (2-propenal, 2-propenoic acid) of particle size of about 10 to 2000 microns was milled using a fluid energy mill to provide a particle size less 10 than 5 microns with the majority of the sample by weight having a particle size of less than 1 micron. The fluid energy or jet mill produces size reduction as a result of high velocity collisions between particles of the process material. The interior of the chamber allows recirculation of oversized particles. 15 Part (b) - Preparation of feed mixture Finely divided particulate poly(2-propenal, 2-propenoic acid) produced according to the process of claim 1 were mixed with granular pig feed using a Tumble or Turbula mixer. The particulate poly-propenal, 2-propenoic acid) was rapidly distributed onto the surface of animal feed granules. There was 20 little if any difference in appearance between the pig feed with and without the added antimicrobial active. Part (c) - Absorption onto water soluble carrier Micronised poly(2-propenal, 2-propenoic acid prepared according to Part a 25 was adsorbed onto water soluble solid carrier using the components and process described below.
WO 2009/009828 PCT/AU2008/001032 8 Microsuspension Component Amount Micronised poly (2-propenal, 2-propenoic acid) 5.0 g Lactose (AR grade) 5.0g Carrageenan Type II 1.0 g Sodium Chloride 1.0 g Glycerin 3% w/w q.s 100.0 ml Carrageenan (a sulfated polysaccharide extracted from seaweeds) and sodium chloride were triturate together to a fine size in a mortar (approximately 5 < 100 um), then added gradually with stirring (speed 5) to 70 ml of 3% glycerin solution. After 45 minutes of stirring this gave very fine dispersion, with no lump. (Appearance was transparent - slight milky). Micronised poly(2-propenal, 2-propenoic acid) and lactose were also triturated 10 together in a separate mortar and added to above dispersion with stirring (speed 7). After complete addition the mortar was washed with 20 ml of the 3% glycerin solution that was added to above dispersion. Rest of 10 ml of 3% glycerin was used to wash the fine powder adhere on the 15 edges of the main containers that splashed during the addition. The stirring wash continued for another two hours to ensure complete mixing. Finally, it is understood that various other modifications and/or alterations may 20 be made without departing from the spirit of the present invention as outlined herein.
Claims (18)
1. A biocidal composition comprising fine particles comprising polyacrolein wherein at least 90% by weight of particles are of a size no more than 5 30 microns.
2. A biocidal composition according to claim 1 wherein at least 90% by weight of particles are of size no more than 5 microns. 10
3. A biocidal composition according to claim 1 wherein the composition is in the form of an aqueous suspension comprising the fine particles of polyacrolein.
4. A biocidal composition according to claim 1 wherein the particles are 15 solid particles and have been reduced in size by milling preferably from a particle size greater than 10 microns.
5. A biocidal composition comprising water dispersible particles comprising a particulate water soluble material and associated therewith biocidal 20 particles comprising polyacrolein wherein at least 90% by weight of particles are of a size no more than 30 microns.
6. A biocidal composition according to any one of the previous claims wherein 90% by weight of biocide particles are of size no more than 25 200nm and most preferably no more than 150nm.
7. A biocidal composition according to any one of the previous claims wherein the polyacrolein is selected from the group consisting of acrolein homopolymers and copolymers comprising no more than 10% 30 by weight of monomers other than acrolein.
8. A biocidal composition according to any one of the previous claims wherein the polyacrolein is oxidized so as to modify the polymer to include from 0.5 to 5 mole carboxyl groups per kilogram of polymer. WO 2009/009828 PCT/AU2008/001032 10
9. A biocidal composition according to any one of the previous claims wherein the particulate biocide composition comprises at least 25%, by weight of polyacrolein based on the total weight of the particle 5 composition.
10. A biocidal composition according to claim 5 wherein the solid particulate carrier for the particulate biocide has a particle size substantially greater than the biocide particles comprising polyacrolein. 10
11. A biocidal composition according to claim 10 wherein the particulate carrier has a particle size in the range of from 30 to 2000 microns.
12. The biocidal composition according to any one of claims 5 and 11 15 wherein formulation includes one or more additives selected from the group consisting of dispersants, surfactants, fillers such as clays and metal salts, water soluble materials, thickeners and the like.
13. A biocidal composition according to any one of the previous claims 20 wherein the particulate biocide comprising polyacrolein is adsorbed onto a carrier which is preferably a water soluble particulate carrier more preferably selected from saccharides, sugar alcohols and water soluble salts. 25
14. A method of preparing a particulate polyacrolein biocidal composition comprising milling a solid comprising polyacrolein to reduce the particle size so that at least 90% by weight of particles are of a size no more than 30 microns. 30
15. A method according to claim 14 wherein the solid is milled to provide at least 90% by weight of particles are of size no more than 5 microns WO 2009/009828 PCT/AU2008/001032 11
16. A method according to claim 14 or claim 15 wherein milling is carried out on the solid or a dispersion of the solid in a liquor in which the particulate polyacrolein is insoluble. 5
17. A method according to any one of claims 14 to 16 wherein the biocide comprising polyacrolein is milled from a composition having a particle size greater than 50 microns to provide a particle size wherein at least 90% by weight of particles are of size no more than 5 microns. 10
18. A method of preparing a particulate biocide containing polyacrolein in accordance with claim 1 or claim 2 the method comprising: (i) forming a solution of polyacrolein in a solvent at least partly soluble in water; and (ii) mixing the solution of polyacrolein with an aqueous solution to 15 provide a fine suspension of polyacrolein particles in the aqueous composition
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US92996107P | 2007-07-19 | 2007-07-19 | |
| US60/929,961 | 2007-07-19 | ||
| PCT/AU2008/001032 WO2009009828A1 (en) | 2007-07-19 | 2008-07-18 | Biocidal polyacrolein composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU2008278272A1 true AU2008278272A1 (en) | 2009-01-22 |
Family
ID=40259213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2008278272A Abandoned AU2008278272A1 (en) | 2007-07-19 | 2008-07-18 | Biocidal polyacrolein composition |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20100266653A1 (en) |
| EP (1) | EP2173165A4 (en) |
| JP (1) | JP2010533654A (en) |
| CN (1) | CN101801181A (en) |
| AU (1) | AU2008278272A1 (en) |
| WO (1) | WO2009009828A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011047421A1 (en) * | 2009-10-19 | 2011-04-28 | Chemeq Ltd | Antifungal composition and method of treatment of dermatitis |
| CN112300307A (en) * | 2019-07-25 | 2021-02-02 | 长沙理工大学 | Preparation method of free radical initiated polyacrylamide and application of free radical initiated polyacrylamide in field of antibacterial materials |
| WO2025129262A1 (en) * | 2023-12-21 | 2025-06-26 | Gramele Industrial Holdings Pty Ltd | Methods of ameliorating microbial growth |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL7901025A (en) * | 1978-02-13 | 1979-08-15 | Technicon Instr | PROCEDURE FOR PREPARING MAGNETICALLY ATTRACTIVE MATERIAL AND PROCEDURE FOR THE IMMUNO DETERMINATIONS TO BE CARRIED OUT THEREFORE. |
| US4413070A (en) * | 1981-03-30 | 1983-11-01 | California Institute Of Technology | Polyacrolein microspheres |
| DE3205487C1 (en) * | 1982-02-16 | 1983-10-13 | Degussa Ag, 6000 Frankfurt | Use of polycondensation products from acrolein and formaldehyde as biocides |
| US4861705A (en) * | 1983-01-31 | 1989-08-29 | Yeda Research And Development Company, Ltd. | Method for removing components of biological fluids |
| JPS61171707A (en) * | 1985-01-28 | 1986-08-02 | Nippon Kayaku Co Ltd | Production of polyacrolein fine particles |
| PH23983A (en) * | 1986-12-23 | 1990-02-09 | Biopolymers Ltd | Biostatic and biocidal composition |
| JPH07138441A (en) * | 1993-09-27 | 1995-05-30 | Nippon Shokubai Co Ltd | Aqueous resin dispersion and its production |
| US5543456A (en) * | 1993-09-27 | 1996-08-06 | Nippon Shokubai Co., Ltd. | Process for preparing an aqueous resin dispersion and an aqueous resin dispersion obtained by the process |
| JPH07278396A (en) * | 1994-04-14 | 1995-10-24 | Nippon Shokubai Co Ltd | Antimicrobial composition |
| EP0645405A1 (en) * | 1993-09-27 | 1995-03-29 | Nippon Shokubai Co., Ltd. | Process for preparing an aqueous resin dispersion and an aqueous resin dispersion obtained by the process |
| DE4404404A1 (en) * | 1994-02-11 | 1995-08-17 | Degussa | Acrolein polymer |
| AUPN327695A0 (en) * | 1995-05-30 | 1995-06-22 | Chemeq Pty. Limited | Chemotherapeutic compositions |
| EP0792895B1 (en) * | 1996-02-22 | 2001-05-16 | Degussa AG | Acrolein releasing copolymers |
| DE19653305A1 (en) * | 1996-12-20 | 1998-08-13 | Degussa | Acrolein-releasing emulsion homopolymers |
| EA003138B1 (en) * | 1998-07-17 | 2003-02-27 | Кемек Лимитид | Aqueous composition based on poly(2-propenal, 2-propenoic acid), method for the preparation the same and use thereof |
| AU2002258649A1 (en) * | 2001-03-30 | 2002-10-28 | Rhodia Inc. | Aqeuous suspension of nanoparticles comprising an agrochemical active ingredient |
| DK1689795T3 (en) * | 2003-11-06 | 2010-06-28 | Chemeq Ltd | Process for producing polyacrolein |
| IL160858A (en) * | 2004-03-14 | 2015-09-24 | Adama Makhteshim Ltd | Nanoparticulate pesticidal composition and a process for its preparation |
-
2008
- 2008-07-18 EP EP08772658A patent/EP2173165A4/en not_active Withdrawn
- 2008-07-18 JP JP2010516327A patent/JP2010533654A/en active Pending
- 2008-07-18 CN CN200880100915A patent/CN101801181A/en active Pending
- 2008-07-18 WO PCT/AU2008/001032 patent/WO2009009828A1/en not_active Ceased
- 2008-07-18 AU AU2008278272A patent/AU2008278272A1/en not_active Abandoned
- 2008-07-18 US US12/669,281 patent/US20100266653A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| CN101801181A (en) | 2010-08-11 |
| JP2010533654A (en) | 2010-10-28 |
| WO2009009828A1 (en) | 2009-01-22 |
| EP2173165A1 (en) | 2010-04-14 |
| US20100266653A1 (en) | 2010-10-21 |
| EP2173165A4 (en) | 2013-03-27 |
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